Certain benzothiazolones and synthesis

ABSTRACT

1. A BENZTHIAZOLONE OF THE FORMULA   2-(O=),3-R4,5-R2,7-R1-2,3-DIHYDROBENZOTHIAZOLE   IN WHICH R1 IS NITRO, TRIFLUOROMETHYL, TRIFLUOROMETHOXY, CHLORINE, BROMINE OR IODINE, R2 IS HYDROGEN, LOWER ALKYL, NITRO, TRIFLUOROMETHYL, TRIFLUOROMETHOXY, CHLORINE, BROMINE, IODINE, FLUORINE, CYANO, FORMYL, CARBOXYL OR CARBOMETHOXY, R4 IS A RADICAL OF THE FORMULA   R5-CO-, R6-OOC-, R7-N(-R8)-CO-, R-SO2- OR H-   R5 IS HYDROGEN, ALKYL WITH 1 TO 12 CARBON ATOMS OPTIONALLY SUBSTITUTED BY CHLORINE, BROMINE OR TRIFLUOROMETHYL, LOWER ALKENYL, OR PHENYL OPTIONALLY CARRYING AT LEAST ONE CHLORINE, BROMINE, TRIFLUOROMETHYL, NITRO OR METHYL RADICAL, R6 IS ALKYL WITH 1 TO 6 CARBON ATOMS OR PHENYL, R7 IS HYDROGEN, ALKYL WITH 1 TO 12 CARBON ATOMS, LOWER ALKOXY-LOWER ALKYL, LOWER ALKENYL, PHENYL, BENZYL OR PHENYLETHYL WITH THE BENZENE RING OPTIONALLY CARRYING AT LEAST ONE CHLORINE, BROMINE, TRIFLUOROMETHYL OR METHYL RADICAL, R8 IS ALKYL WITH 1 TO 12 CARBON ATOMS OR LOWER ALKENYL, AND R9 IS LOWER ALKYL OPTIONALLY SUBSTITUTED BY CHLORINE, BROMINE OR TRIFLUOROMETHYL, PHENYL OPTIONALLY SUBSTITUTED BY AT LEAST ONE CHLORINE, BROMINE, TRIFLUOROMETHYL, NITRO OR METHYL, OR A DIMETHYLAMINO GROUP.

United States Patent ABSTRACT OF THE DISCLOSURE Benzthiazolones of thegeneral formula (R l J in which R is an electronegative radical, R ishydrogen, alkyl or an electronegative radical, R is hydroxy, alkoxy oran aliphatic or cycloaliphatic radical, R is a radical of the formula orhydrogen,

R is hydrogen, alkyl, substituted alkyl, alkenyl, phenyl or substitutedphenyl,

R is alkyl or phenyl,

R' is hydrogen, alkyl, alkoxyalkyl, alkenyl or other aliphatic radical,phenylalkyl, phenyl or substituted phenyl,

R is alkyl, alkenyl, or except when R is hydrogen, hy-

drogen, or

R and R together with the nitrogen to which they are attached form aheterocyclic ring,

R is alkyl, substituted alkyl, phenyl, substituted phenyl ordimethylamino, and

n is 0, 1 or 2,

which possess insecticidal, acaricidal, fungicidal, algicidal andherbicidal properties.

The present invention relates to and has for its objects the provisionof particular new benzthiazolones, wherein an electronegative radical ispresent in the 7- position and a hydrogen, carbonyl or sulfonyl radicalis directly connected to the nitrogen atom, which possess insecticidal,acaricidal, fungicidal, algicidal and herbicidal properties, activecompositions in the form of mixtures of such compounds with solid andliquid dispersible carrier vehicles, and methods for producing suchcompounds and for using such compounds in a new way especially forcombating pests, e.g. insects, acarids, fungi, algae and undesiredplants, especially insects, acarids and fungi, with other and furtherobjects becoming apparent from a study of the within specification andaccompanying examples.

The present invention provides, as new compounds, benzthiazolones of thegeneral formula in which R is an electronegative radical, R is hydrogen,alkyl or an electronegative radical, R is hydroxy, alkoxy or analiphatic or cycloaliphatic radical, R is a radical of the formula I Ris hydrogen, alkyl, substituted alkyl, alkenyl, phenyl or substitutedphenyl,

R is alkyl or phenyl,

R is hydrogen, alkyl, alkoxyalkyl, alkenyl or other aliphatic radical,phenyl or substituted phenyl,

R is alkyl, alkenyl, or except when R is hydrogen, hy-

drogen, or

R and R together with the nitrogen to which they are attached form aheterocyclic ring,

R is alkyl, substituted alkyl, phenyl, substituted phenyl ordimethylamino, and

n is 0, 1 or 2.

These compounds possess strong acaricidal, insecticidal and fungitoxicproperties.

Preferred electronegative radicals R are nitro, trifluoromethyl,trifluoromethoxy, chlorine, bromine, iodine and radicals of the formulaSO Y, in which Y is an aliphatic, cyeloaliphatic, araliphatic oraromatic radical, fluorine or an optionally substituted amino group.

Aliphatic radicals Y are generally those with 1 to 8, preferably loweraliphatic with 1 to 4, carbon atoms, which radicals may be branched. Ofthe cycloaliphatic radicals, those with 5 or 6 carbon atoms in the ringsystem are preferred.

Araliphatic radicals Y contain in the aliphatic chain generally 1 to 4,preferably 1 or 2, carbon atoms and, as the aromatic moiety, preferablythe phenyl radical.

As the aromatic radical Y, the phenyl radical is preferred.

If Y stands for an amino group, one or both hydrogen atoms may bereplaced by a C lower alkyl group or by a 5- or 6-memberedcycloaliphatic radical, or the nitrogen atom may be part of a preferably5- or 6-membered heterocyclic ring which may also contain an oxygenatom, a sulfur atom or a nitrogen atom that may carry a C lower alkylgroup. Furthermore, one of the hydrogen atoms of the amino group Y mayalso be replaced by a phenyl radical.

Alkyl radicals R are preferably lower alkyl with 1 to 4 carbon atoms.

As electronegative radicals R those mentioned under R are suitable, aswell as fluorine, cyano, formyl, or carboxyl, the last-mentionedpossibly being esterified with an aliphatic or araliphatic alcohol orwith a phenol.

When R is esterified carboxy, the preferred esterifying radicals arethose stated as preferred for the aliphatic, araliphatic or aromaticradicals Y.

The aliphatic radicals R are preferably those with 1 to 8, especially 1to 4, carbon atoms; cycloaliphatic radicals R are preferably those with5 or 6 carbon atoms in the ring system. Alkoxy groups R are preferablylower alkoxy containing 1 to 4 carbon atoms.

R is preferably hydrogen, alkyl with 1 to 12 carbon atoms optionallysubstituted by chlorine, bromine or trifluoromethyl, lower alkenyl with2 to 4 carbon atoms or phenyl optionally carrying at least one chlorine,bromine, trifiuoromethyl, nitro or methyl radical.

R is preferably alkyl with 1 to 6 carbon atoms or phenyl.

R' is preferably hydrogen, alkyl with l to 12 carbon atoms, loweralkoXy-lower alkyl With 1 to 4 carbon atoms in each alkyl radical, loweralkenyl with 2 to 4 carbon atoms, phenyl, benzyl or phenylethyl with thebenzene ring optionally carrying at least one chlorine, bromine,trifluoromethyl or methyl radical.

R is preferably hydrogen, alkyl with 1 to 12 carbon atoms, or loweralkenyl with 2 to 4 carbon atoms. However, R and R together with theattached nitrogen atom, may form a 5- or 6-membered ring, preferablypiperidine, pyrrolidine, morpholine or thiomorpholine.

R is preferably lower alkyl with 1 to 4 carbon atoms optionallysubstituted by chlorine, bromine or trifiuoromethyl, phenyl optionallysubstituted by at least one chlorine, bromine, trifluoromethyl, nitro ormethyl, or a dimethylamino group.

The present invention also provides a process for the preparation of asubstituted benzthiazolone of the formula (I) in which one of theparticularly new benzthiozolones of the general formula NH i o s R1 (11)is reacted (a) with an acid chloride of the general formula R -CO--Cl(I11) (b) with a chloroformic acid alkyl ester or chloroformic acidphenyl ester of the general formula -R O--COCl (IV) or (c) with asulfonyl chloride of the general formula R -SO Cl (V) or (d) in which a2-carbamyl-benzthiazole-N-oxide-3 of the formula u--N)O I OON/ S isreacted with phosphorus oxychloride; in which formulas (II) to (VI), R RR R R R R R and n possess the meanings stated above.

The benzthiazolones of the general formula (I), in comparison with knowncommercial products of the same directions of activity, possess a higheracaricidal, insec ticidal and fungitoxic activity. The active compoundstherefore represent a genuine enrichment of the art.

If, according to process variant (a), S-trifluoromethyl-7-nitro-benzthiazolone and methacrylic acid chloride, for example, areused as starting materials, the reaction course can be represented bythe following equation:

Similarly, process variant (b) may be illustrated by the followingequation:

F30 NH J: 01-00011; 0

(IIc) (IVa) F36 I I-000011,

(27) (VIII) If, according to process variant (0),5-nitro-7-trifluoromethyl-benzthiazolone and methanesulfochloride areused as starting materials, the reaction course is illustrated by thefollowing equation:

An example of the process variant (d) is the reaction of 2 nbutylcarbamyl-5-trifluoromethyl-7-nitro-benzthiazole-N-oxide-3 withphosphorus oxychloride, which proceeds as follows:

The benzthiazolones of the formula (II) required as starting materialsare new. They can be prepared according to a process that has not beenhitherto described in the prior art, from the suitably substitutedZ-carbamyl-benzthiazole-N-oxides-B by contact with phosphorusoxychloride at temperatures between about 20 and 160 0., preferably fromabout 50 to C., according to the following equation:

As examples of the benzthiazolones of the formula (II), there may bementioned 5-trifluoromethyl-7-nitro-, 5 nitro-7-trifluoromethyland5,7-bi.s(trifluoromethyl)- benzthiazolones.

The acid chlorides of the formula (III) to be used as starting materialshave been described in the literature. As examples, there may bementioned: acetyl, trifluoroacetyl, propionyl, u-chloropropionyl,n-butyryl, acrylic acid, methacrylic acid, dimethylacrylic acid,crotonyl, pchlorobenzoyl, o-nitro-benzoyl and toluyl chlorides.

The chloroformic acid esters of the formula (IV) are likewise alreadyknown. As examples, there may be mentioned: chloroformic acid isopropyl,methyl, ethyl, nbutyl, n-hexyl and phenyl esters.

The compounds (V) to be used as starting materials are also known fromthe literature. There may be mentioned, for example: methane-,chloromethaneand B- chloroethanesulfonyl chlorides, and benzene-,3,4-dichlorobenzeneand 2-chlorobenzene-sulfochlorides.

As solvents and diluents predominantly suitable for the process variants(a) to (c) are inert organic solvents. These include hydrocarbons, suchas benzene, chlorobenzene, toluene, and xylene; ethers, such as diethylether, dibutyl ether, tetrahydrofurane and dioxane; esters, such asethyl acetate; ketones, for example acetone and methylethyl ketone; andnitriles, such as acetonitrile and propionitrile.

The process variants (a) to (c) are usually so carried out that thebenzthiazolone concerned of the general formula (II) is provided in oneof the said solvents in the presence of an acid-binding agent,preferably a tertiary amine, such as triethylamine,N,N-dimethylbenzylamine, diethylaniline, pyridine, picoline orquinoline, or an alkaline-reacting inorganic substance such as potassiumor sodium carbonate, and the appropriate reactive chlorine compound ofthe formula (III), (IV) or (V) is added incrementally to the reactionmixture, with stirring.

The starting materials are preferably used in stoichiometricproportions.

The reaction temperature can be varied within a fairly wide range. Ingeneral, the work is carried out at from about -10 to +80 C., preferablyat from about 10 to 40 C.

The working up of the reaction mixture may be carried out according tocustomary methods.

The purification of the reaction products can, if desired, be effectedby recrystallization from organic solvents, especially from alcoholssuch as methanol or ethanol.

As already mentioned, the compounds according to the invention aredistinguished by outstanding acaricidal, insecticidal and fungitoxicproperties. They possess a good efiiectiveness against both sucking andbiting insects, Diptra and mites, including a marked ovicidal andsystemic activity. In addition, they are algicidally, and in higherapplied amounts herbicidally, effective. They also exhibitanti-bacterial activity.

By reason of these properties, the new products may be used with successin crop protection against the most diverse animal pests as well as forthe control of seedborne and soil-borne fungal diseases of plants.

To the sucking insects contemplated herein there belong, in the main,aphids (Aphidae) such as the green peach aphid (Myzus persicae), thebean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi),the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphumsolanifolii), the currant gall aphid (Cryptomyzus korschelti), the rosyapple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterusarundinis) and the cherry black-fly (Myzus cerasi); in addition, scalesand mealybugs (Coccina), for example the oleander scale (Aspidiotushederae) and the soft scale (Lecanium hesperiaum) as well as the grapemealybug (Pseudococcus maritimus); thrips (T hysanoptera), such asHercinothrips femoralis, and bugs, for example the beet bug (Piesmaquadrata), the red cotton bug (Dysdercus intermedius), the bed bug(Cimex lectularius), the assassin bug (Rhodnius prolixus) and Chagas bug(T riatoma infestans) and, further, cicadas, such as Euscelis bilobatusand Nephotettix bipunctatus; and the like.

In the case of the biting insects contemplated herein, above all thereshould be mentioned butterfly caterpillars (Lepidoptera) such as thediamond-back moth (Plutella maculipennis), the gypsy moth (Lymantriadispar), the browntail moth (Euproctis chrysorrhoea) and tentcaterpillar (Malacosoma neustria); further, the cabbage moth (Mamestrabrassicae) and the cutworm (Agrotis segetum), the large white butterfly(Pieris brassicae), the small winter moth (Cheimatobia brumata), thegreen oak tortrix moth (Tortrix viridana), the fall armyworm (Laphygmafrugip'erda) and cotton worm (Prodenia litura), the ermine moth(Hypohomeuta padella), the Mediterranean flour moth (Ephestiakilhniella) and greater wax moth (Galleria mellonella); and the like.

Also to be classed with the biting insects contemplated herein arebeetles (Coleoptera), for example the granary weevil (Sitophilusgranarius=Calandra granaria), the Colorado beetle (Leptinotarsadecemlineara), the dock beetle (Gastrophysa viridula), the mustardbeetle (Phaedon cochleariae), the blossom beetle (Meligethes aeneus),the raspberry beetle (Byturus tomentosus), the bean weevil (Bruchidius=Acanthoscelides obtectus) the leather beetle (Dermestes frischi), thekhapra beetle (T roguderma granarium), the flour beetle (Triboliumcastaneum), the northern corn billbug (Calandra or Sitophilus zeamais),the drugstore beetle (Stegobium paniceaum), the yellow mealworm(Tenebrio molitor) and the sawtoothed grain beetle (Oryzaephilussurinamensis), and also species living in the soil, for examplewireworms (Agriotes spec.) and larvae of the cockchafer (Melolonthamelolontha); cockroaches, such as the German cockroach (Blattellagermanica), American cockroach (Periplaneta americana), Madeiracockroach (Leucophaea or Rhyparobia maderae), oriental cockroach (Blattaorienrllis), the giant cockroach (Blaberus giganteus) and the blackgiant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta;further, Orthoptera, for example the house cricket (Acheta domesticus);termites such as the eastern subterranean termite (Reticulitermesflavipes) and Hymenoptera such as ants, for example the garden ant(Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such asthe vinegar fly (Drasophila melanogaster), the Mediterranean fruit fly(Ceratitis capitata), the house fly (Musca domestica), the little housefly (F annia canicularis), the black blow fly (Phormia regina) andbluebottle fly (Calliphora erythrocephala) as well as the stable fly(Stomoxys calcitrans); further, gnats, for example mosquitoes such asthe yellow fever mosquito (Aedes aegypti), the northern house mosquito(Culex pipiens) and the malaria mosquito (Anopheles stephensi); and thelike.

With the mites (Acari) contemplated herein there are classed, inparticular, the spider mites (Tetranychidae) such as the two-spottedspider mite (Tetranychus telarius: Tetranychus althaeae or Tetranychusurticae) and the European red mite (Paratetranychus pil0sus=Pan0nychusulmi), gall mites, for example the black currant gall mite (Eriophyesribis) and tarsonemids, for example the broad mite (Hemitarsonemuslatus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, suchas the relapsing fever tick (Ornithodorus moubata); and the like.

-When applied against hygiene pests and pests of stored products,particularly flies and mosquitoes, the compounds of the invention arealso distinguished by an outstanding residual activity on wood and clay,as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)pesticide diluents or extenders, i.e. diluents, carriers or extenders ofthe type usable in conventional pesticide formulations or compositions,e.g. conventional pesticide dispersible carrier vehicles such as gases,solutions, emulsions, suspensions, emulsifiable concentrates, spraypowders, pastes, soluble powders, dusting agents, granules, etc. Theseare prepared in known manner, for instance by extending the activecompounds with conventional pesticide dispersible liquid diluentscarriers and/or dispersible solid carriers optionally with the use ofcarrier vehicle assistants, e.g. conventional pesticide surface-activeagents, including emulsifying agents and/or dispersing agents, whereby,for example, in the case Where water is used as diluent, organicsolvents may be added as auxiliary solvents. The following may bechiefly considered for use as conventional carrier vehicles for thispurpose: aerosol propellants which are gaseous at normal temperaturesand pressures, such as freon; inert dispersible liquid diluent carriers,including inert organic solvents, such as aromatic hydrocarbons (e.g.benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated,especially chlorinated, aromatic hydrocarbons (e. g. chlorobenzenes,etc.), cycloalkanes (e.g. cyclohexane, etc.), paraflins (e.g. petroleumor mineral oil fractions) chlorinated aliphatic hydrocarbons (e.g.methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol,ethanol, propanol, butanol, glycol, etc.) as well as ethers and estersthereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine,etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethylsulfoxide, etc.), ketones (e.g. acetone, methyl ethyl ketone, methylisobutyl ketone, cyclohexanone, etc.), and/or water; as well as inertdispersible finely divided solid carriers, such as ground naturalminerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calciumcarbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) andground synthetic minerals (e.g. highly dispersed silicic acid,silicates, e.g. alkali silicates, etc.); whereas the following may bechiefly considered for use as conventional carrier vehicle assistants,e.g. surfaceactive agents, for this purpose: emulsifying agents, such asnon-ionic and/ or anionic emulsifying agents (e.g. polyethylene oxideesters of fatty acids, polyethylene oxide ethers of fatty alcohols,alkyl sulfates, alkyl sulfonates, aryl sulfonates, etc., and especiallyalkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.);and/or dispersing agents, such as lignin, sulfite waste liquors, methylcellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/ or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other insecticides,acaricides, rodenticides and fungicides, or bactericides, nematocides,herbicides, fertilizers, growth-regulating agents, etc., if desired, orin the form of particular dosage preparations for specific applicationmade therefrom, such as solutions, emulsions, suspensions, powders,pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 01-95% by weight, andpreferably 05-90% by weight, of the mixture, whereas carrier compositionmixtures suitable for direct application or field application generallycontemplate those in which the active compound is present in an amountsubstantially between about 0.000l-%, preferably 0.01-1%, by weight ofthe mixture. Thus, the present invention contemplates over-allcompositions which comprises mixtures of a conventional dispersiblecarrier vehicle such as (1) a dispersible inert finely divided carriersolid, and/ or (2) a dispersible carrier liquid such as an inert organicsolvent 7 and/ or water preferably including a surface-active effectiveamount of a carrier vehicle assistant, e.g. a surfaceactive agent, suchas an emulsifying agent and/or a dispersing agent, and an amount of theactive compound which is effective for the purpose in question and whichis generally between about 0.000l;%, and preferably 0.0195%, by weightof the mixture.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50- microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/ hectare are needed,and often amounts only up to about 15 to 1000 g./hectare, preferably 40to 600 g./ hectare, are sufficient. In this process, it is possible touse highly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95,% by weight of the activecompound or even the 100% active substance alone, e.g. about 20-100% byweight of the active compound.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. insects, acarids, fungi,algae and undesired plants, and more particularly methods of combatingat least one of the insects, acarids and fungi which comprise applyingto at least one of correspondingly (a) such insects, (b) such acarids,(c) such fungi, (d) such algae, (e) such undesired plants and (f) thecorresponding habitat thereof, i.e. the locust to be protected, acorrespondingly combative or toxic amount, i.e. an insecticidally,acaricidally, fungicidally, algicidally or herbicidally effective amountof the particular active compound of the invention alone or togetherwith a carrier vehicle as noted above. The instant formulations orcompositions are applied in the usual manner, for instance by sprayingatomizing, vaporizing, scattering, dusting, watering, squirting,sprinkling, pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The process of the present invention is illustrated in and by thefollowing preparative Examples.

FaC NH I IO2 (H3) 307 g. (1 mole) of2-carbamyl-5-trifiuromethyl-7-nitrobenzthiazole-n-oxide-3 are suspendedin 300 cc. of anhydrous toluene. To this suspension there are slowlyadded dropwise at 90 to 100 C., with stirring, 153 g. (1 mole) ofphosphorus oxychloride. The reaction mixture is stirred for a further 4hours at 100 to C. after completion of the dropwise addition, and theprecipitated polycyanic acid is filtered off hot. During cooling of thefiltrate, 216 g. (82% of theory) of5-trifluoromethyl-7-nitro-benzthiazolone crystallize in the form ofcolorless needles. The product is filtered off with suction and washedwith water until there is a neutral reaction. The compound has a meltingpoint of 208 to 210 C.

Analysis.C H F N O S (molecular weight 264.5).

153.5 g. (0.5 mole) of2-carbamyl-S-nitro-7-trifiuoromethylbenzthiazole-N-oxide-3 are suspendedin 700 cc. of anhydrous toluene and reacted, under the conditions statedin (a), with 76.5 g. (0.5 mole) of phosphorus oxychloride. Aftercompletion of the reaction and cooling of the mixture, the precipitatedproduct is filtered OE With suction and the residue on the filter iswashed with water until there is a neutral reaction. For purification,the crystalline product obtained can be recrystallized from ethanol. 100g. (76% of theory) of 5-nitro-7-trifiuoromethylbenzthiazolone areobtained in the form of colorless needles with a melting point of 247 to248 C.

132 g. (0.4 mole) of 2-caIbamyl-5,7 bis(trifluoromethyl)benzthiazo1e-N-oxide-3 are reacted in 400 cc. oftoluene with 61.2 g. (0.4 mole) of phosphorus oxychloride under the sameconditions as in (a). The precipitated polycyanic acid is filtered otfhot and the solvent is removed under reduced pressure. The residue iswashed with water until there is a neutral reaction and is thenrecrystallized from dilute ethanol 98 g. (86% of theory) of5,7-bis-(trifluoromethyl)benzthiazolone are obtained in the form ofshiny, almost colorless flakes of the melting point 138 to 139 C.

Analysis.C H F ,-NOS (molecular weight 287.2).

C H F N S Calc., percent 37. 6 1. 1 39. 7 4. 9 5. 6 11. 1 Found, percent37. 4 1. 4 39.2 5. 3 5.5 11.6

EXAMPLE 2 F30 III-C O-NH-i-C4H9 V \s )=o l N 02 72.6 g. (0.2 mole) of 2isobutylcarbamyl-S-trifluoromethyl-7-nitro-benzthiazole-N-oxide-3 aredissolved in 400 cc. of anhydrous benzene and 30.6 g. (0.2 mole) ofphosphorus oxychloride and the mixture is boiled for 3 hours underreflux. The solvent is then removed under reduced pressure, and theresidue is recrystallized from ethanol. There are obtained 44 g. (60% oftheory) of 3-N- (isobutylaminocarbonyl)-5-trifluoromethyl-7-nitrobenzthiazolone in the form of colorless needles of the melting point 104to 105 C.

Analysis.C H F N O4S (molecular weight 363.1).

C H F N O S Calm, percent 43.0 3.3 15.7 11.3 17. 6 8. 8 Found, percent43. 1 3. 8 15. 5 11. 6 18.0 7. 9

10 In an analogous manner to that described above, the followingbenzthiazolones were prepared from the corresponding2-substituted-carbamyl-benzthiazole-N-oxides-3:

FaC N-O O-NH-CH:

m.p.: 150 with decomposition F C N-C O-NH-CzHs m.p.: 125 withdecomposltlon F30 N-C 0-NH-C3H1 S O 1 N02 m.p.: 91-92 C. withdecomposition F30 -N-C ONH-i-C 3H1 m.p.: 82-83 C. with decomposition F 0N-CON(CH3)2 s O I N 2 m.p.: 149-150 C.

FaC N-C ONHO Ha C Fa F 0 N-C O-NH-CaHs C Fa m.p.: 96-99 C.

01 N-C ONHC2H5 m.p.: 129-130 C.

01 N-C O-NH-C3H1 Cl N-C O-NH-l-C3H1 0 I S N 02 m.p.: 111-112 o.

C1 NC O--NHC4H9 C1 N-C O-NHi-C Hn N-C O-NH-C4H O S N 02 (14) F 0 N-CO-NHOHgCHz0CH3 m.p.: IDS-104 0. F30 I N-C ONH-OH,-

m.p.: 112113 C.-

FzC- N-C ONHCHCH=CH2 m.p.:103-104" C;

OzN N-C O-NH-CE C Fa (18) m.p.: 120-121 0., with decomposition;

OgN N -C O--NHCzH o F; r (19 m.p.: IOU-101 0., with decomposition.

OzN- N--O O-NH-i-C 4H9 C Fa (20) EXAMPLE 3 F30 NC O 0 GzHa 264 g. (1mole) of 5-trifluoromethyl-7-nitro-benzthiazolone and 101 g. -(1 mole)of triethylamine are d1ssolved in 1200 cc. of acetone. To this solutionthere are added dropwise at 20 to 40 C., with stirring, 108 g. (1 mole)of chloroformic acid ethyl ester. The reaction mixture is stirred for afurther 3 hours at 20 to 30 C. and the mixture is then poured into icewater; the precipitated product is filtered off with suction and it iswashed with Water. After recrystallization from ethanol, 295 g. (88% oftheory) of 3-N-(ethoxycarbonyl)-5-trifiuoromethyl-7-nitro-benzthiazolone are obtained in the form of colorless needles ofthe melting point 100 to 101 C.

Analysis.C H F N O S (Molecular Weight 336.1).

02.10., percent Found, percent corto s

men 0 FaC N-C O 0 CH3 m.p. 137138 C.

F 0 N-C O O CaH7 m.p.: -97 C.

NC O O CoHia FaC N-C O 0 CH3 F30 N-C O O CzHli i C F3 ON N-SOzCHzCl l CF;

m.p.: 122-124? C.

mp: 188189 C.

FzC N-C OCH:

m.p.: 149-151" C.

EXAMPLE 4 Tetranychus test (T. urticae/phosphoric-acid-ester resistant)Solvent: 3 parts by weight dimethyl formamide Emulsifier: 1 part byweight alkylarylpolyglycol ether To produce a suitable preparation ofactive compound, 1 part by weight of the active compound is mixed withthe stated amount of solvent containing the stated amount of emulsifierand the concentrate so obtained is diluted with water to the desiredconcentration.

Bean plants (Phaseolus vulgaris), which have a height of approximately-30 cm., are sprayed with the preparation of the active compound untildripping wet. These bean plants are heavily infested with spider mites(Tetranychus urticae) in all stages of development.

After the specified periods of time, the effectiveness of thepreparation of active compound is determined by counting the dead mites.The degree of destruction thus obtained is expressed as a percentage:100% means that all the spider mites are killed whereas 0% means thatnone of the spider mites are killed.

The active compounds, the concentrations of the active compounds, theevaluation times and the results can be seen from the following Table 1:

TABLE 1 [Tetra'nychus urticac test] Degree of destruction in percentafter 2 days Concentration of active compound in percent CH3 C1 (known)TABLE 1C0ntinued [Tetranychus urticae test] Concen- Degree of trntiondestrucof active tion in compercent pound in after 2 Active compoundpercent days (B) S 0 Hz 0 0. 2 95 II 0. 02 0 CH=N O-C-NH-CHs 0 Ha(known) (41) 0. 2 100 OzN -NC OCzHs 0.02 98 S O C Fa (37)-.. 0. 2 100F50 --NC 0 0211 0.02 100 N O a (38).-- 0. 2 100 Fa C N-C 0 03115 0. 0298 (22) 0. 2 100 F30 N-COOCHa 0.02 95 (33) 0. 2 100 OzN N--C 0 0 0 H 0.02 98 0. 002 60 (32)... 0. 2 100 OzN NC O 0 CH3 0. 02 100 (21)--. 0. 2100 FaC N-C O 0 C211; 0. 02 100 0. 002

(34) 0. 2 100 F 0 N-C O 0 0 11 0. 02 0. 002 60 0 0. 002 60 s (23).-. 0.2 FaC -N-COOC:H1 0. 02 99 (35).... 0. 2 100 OzN --N-C O O-i-C H1l 0. 02100 TABLE 1-Continued [Tetranvchus urticae test] Concen- Degree 01tratlon destrucof active tion in compercent pound in after 2 Activecompound percent days (24)--. 0. 2 100 FIG N-C O-l-CsHz 0. 02 100(29)--. 0. 2 100 FaC N-C O O-i-CsH7 0. 02 80 (25)--. r 0. 2 100 13c N-C0 0 C4H 0. 02 98 0. 002 80 26 0. 2 100 FsC N-COOCaHrs 0.02 98 0. 002 70(3).-.. v 0. 2 100 FsC N--C O-NH-CzHs 0. 02 80 (s)-;.- 0.2 100 E30 N-CO-NH-CzHa 0. O2 90 (14)-.. 0. 2 100 Fr) N-C O-NH-CrHo 0. 02 100 (1)..-.0. 2 100 FaC N-C O-NH-l-Cfilo 0. 02 50 (47) 0. 2 100 E N-S 020E201 0.02100 EXAMPLE 5 resistant) Solvent: 3 parts by weight dimethyl formamideEmulsifier: 1 part by weight alkylarylpolyglycol ether To produce asuitable preparation of active compound, 1 part by weight of the activecompound is mixed with the stated amount of solventcontaining the statedamount of emulsifier and the concentrate so obtained is dilutedwithwater'to 'the desired concentration.

Bean plants (Phaseolus vulgarrs), which have a height of approximately10-30 cm., are sprayed with the prep aration of the active compounduntil dripping wet. These bean plants are heavily infested with spidermites (Tetranychus telarius) in all stages of development.

After the specified periods of time, the effectiveness of thepreparation of active compound is determined by counting the dead mites.The degree of destruction thus obtained is expressed as a percentage:100% means that all the spider mites are killed whereas 0% means thatnone of the spider mites are killed.

The active compounds, the concentrations of the active compounds, theevaluation times and the results can be seen from the following Table 2:

TABLE 2 v T. mum's test] Ooncen- Degree of nation destrucof active tionin compercent pound in alter 2 Active compound percent days (A)-.- CH;0. 02 o. 004 0 NCH=N (known) (32).-. 0. 02 OaN NOO OCH: 0. 004 30(35)... 0. 02 100 OzN N-C 0 0-l-C3H1 0. 004 98 \5 o l 0 Fl EXAMPLE 6Plutella test Solvent: 3 parts by weight dimethyl formamide Emulsifier:1 part by weight alkylaryl polyglycol ether To produce a suitablepreparation of active compound, 1 part by weight of the active compoundis mixed with the stated amount of solvent containing the stated amountof emulsifier and the concentrate is diluted with water to the desiredconcentration.

Cabbage leaves (Brassica pleracea) are sprayed with the preparation ofthe active compound until dew moist and are then infested withcaterpillars of the diamond-. back moth (Plutella maculipennis).

After the specified periods of time, the degree of destruction isdetermined as a percentage: 100% means that all the caterpillars arekilled whereas 0% means that none of the caterpillars are killed.

The active compounds, the concentrations of the active compounds, theevaluation times and the results can be seen from T able 3:

TABLE 3 [Plntelle test] I Active compound TABLE 3--C0ntinued Concen-Degree of tration destruc- Concen- Degree of of active tion in trationdestrucccmpercent of active tion in 5 pound in after 2 compercent Activecompound percent days pound in after 2 4a I 0.2 100 days FaC N-S 01cm0.02 100 EXAMPLE 7 Doralis test (systemic action) 0, 2 100 Solvent: 3parts by weight dimethyl formamide Emulsifier: 1 part by weightalkylarylpolyglycol ether To produce a suitable preparation of activecompound, 1 part by weight of the active compound is mixed with thestated amount of solvent containing the stated amount of emulsifier, andthe concentrate is diluted with water to the desired concentration. 100Bean plants (Vicia faba) which have been heavily intested with the beanaphid (Doralis fabae) are watered with the preparation of the activecompound so that the preparation of active compound penetrates into thesoil without wetting the leaves of the bean plants. The active compoundis taken up by the bean plants from the soil and thus reaches theinfested leaves. 0 2 100 After the specified period of time, the degreeof deb struction is determined as a percentage. means that all theaphids are killed; 0% means that none of the aphids are killed. 35 Theactive compounds, the concentrations of the active compounds, theevaluation time and the results can be seen from the following Table 4:

TABLE 4 [Doralis test/systemic action] Concentration 0! ac- Degree oftive comdestruction pound in in percent Active compound percent after 4days (A).-- cm 0.2 o

NCH=N CH:

(known) (B)...-. CI 1| 0 /N-CH=N 0CNH-CH| CH3 (known) FaC N-C O-NH-O H:

FsC- --N-C O-NHCH2 Fac- --No O-NH-CzHa TABLE 4-Continued Concentrationof ac- Degree of tive comdestruction pound in in percent percent after 4days It will be appreciated that the instant specification and R is aradical of the formula examples are set forth by way of illustration andnot limitation, and that various modifications and changes may be madewithout departing from the spirit and scope of the 60 present invention.

What is claimed is: 1. A benzthiazolone of the formula in which R isnitro, trifluoromethyl, tridinoromethoxy, chlorine,

bromine or iodine,

R is hydrogen, lower alkyl, nitro, trifluoromethyl, trifiuoromethoxy,chlorine, bromine, iodine, fluorine, cyano,

formyl, carboxyl or carbomethoxy,

, SO -R or hydrogen R is alkyl with 1 to 12 carbon atoms or loweralkenyl,

and

R is lower alkyl optionally substituted by chlorine, bromine ortrifluoromethyl, phenyl optionally substituted by at least one chlorine,bromine, trifluoromethyl, nitro or methyl, or a dimethylamino group. 2.A benzthiazolone according to claim 1 in which R is a radical of theformula -CO-R CO-OR or hydrogen.

3. A benzthiazolone according to claim 1 in which R is lower alkyl,nitro, trifluoromethyl, trifiuoromethoxy,

chlorine, bromine, iodine, fluorine, cyano, formyl, carboxyl, orcarbomethoxy, and R is alkyl with 1 to 6 carbon atoms.

4. The compound according to claim 1 wherein such compound is3-N-(carbethoxy)-S-trifiuoromethyl-7-nitrobenzthiazolone of the formula5. The compound according to claim 1 wherein such compound is 3N-(carbobutoxy)-S-trifluoromethyl-7-nitrobenzthiazole of the formula 6.The compound according to claim 1 wherein such compound is 3N-(carbohexoxy)-5-trifiuoromethyl-7-nitrobenzthiazolone of the formula FN-COOCgHn 7. The compound according to claim 1 wherein such compound is3 N-(carbisopropoxy)--nitro-7-trifiuoromethylbenzthiazolone of theformula 8. The compound according to claim 1 wherein such compound is3-N- (methanesulfo 5-trifluoromethyl-7-nitrobenzthiazolone of theformula References Cited UNITED STATES PATENTS 3/1972 OAmico 260-3045/1972 Umio 2'60304 OTHER REFERENCES Postovskll et a1.; Chem.Abls'tracts, 49:1011 (1953).

RICHARD J. GALLAGHER, Primary Examiner US. Cl. X.R.

P0405) UNITED STA'T'TSS PATENT OFFICE CERTIFICATE 0F CORRECTIONPatentNo. 3,839,349 Dated October 1, 1974 Inventofls) Kblaus Wagner etal (Page 1 of 2) It: is certified that error appearsin theaboye-identified patent and that said Letters Patent are herebycorrected as shown below:

Col. 5, line 54, correct spelling of .Dipteafa" 001.9, line 41, after"ethanol" insert a period Col. 11, compound (20) cancel the structuralformula and substitute cn ooc --co m 1 c H 549" Col. 12, line 16,"Found, percent", under heading "C" cancel "39.4" and substitute 39.5

Col. 14, compound (45) in the structural formula, cance1' '(CH andsubstitute (CH I Col. 16, compound (38) cancel "H and substitute H Col;16, compound (34) cancel "F 6" and substitute O N Col. 16, line 60,after compound (34), cancel last line offigures reading "0.002 60".

Po-mso UNITED S'IA'IES PATENT OFFICE CERTIFICATE OF CORRECTION PatentNo. 3,859,349 Dated October l, 1974 Invencor(s) (page 2 of 2) It: iscertified that: error appearsin the aboye-idencified patent and that:said Letters Patent are hereby corrected as shown below:

C01. 21, compound (12), in the structur al formula,

- I! 6 u cancel 0 H and substltute C H Signed and sealed this 1st day ofApril 1975.

(SEAL) \ttesti v C.- Z'IARSHALL DA-Nh Commissioner of Patents EASO LT} Cand Trademarks Attesting uficer

1. A BENZTHIAZOLONE OF THE FORMULA